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Premelting and the Machanisms of Melting in the Alkali Halides

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posted on 2021-11-08, 21:48 authored by Tallon, Jeffery Lewis

An experimental and theoretical study of premelting behaviour and mechanisms of melting in the alkali-halides is presented. Theories of melting and previous premelting experiments are first reviewed, then an elastic strain theory of melting is developed, which includes dilatation and shear contributions to the elastic energy and to the vibrational entropy, as well as a communal entropy and an entropy due to the isothermal expansion on melting. By fitting experimental melting parameters, dislocation-like local strains are implicated. The bulk and shear moduli are shown to be continuous with respect to dilatation through the melting expansion and one of the shear moduli vanishes at the dilatation of the melt at the melting temperature. A modified Born instability theory of melting is thus valid. Premelting rises in the apparent specific heat and electrical conductivity within 6 K of the melting point are studied and are shown to occur at the surfaces only. The use of guard rings to eliminate surface conduction is essential at all temperatures above the extrinsic/intrinsic conductivity 'knee', and electrical fringing must be taken into account for typical specimen sizes. For various surface orientations, the rises in surface conductivity occur at lower temperatures the lower the surface packing density, and for deformed specimens, the greater the deformation. The results are interpreted in terms of an atomic-scale surface melting below the melting point, and a consequent rapid rise in vaporisation rate. A dislocation theory of surface melting, melting and the solid-liquid interface is developed which gives good agreement with experimental values for the melting temperatures and the interfacial energies.


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Date of Award



Te Herenga Waka—Victoria University of Wellington

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Author Retains Copyright

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Degree Grantor

Te Herenga Waka—Victoria University of Wellington

Degree Level


Degree Name

Doctor of Philosophy

Victoria University of Wellington Item Type

Awarded Doctoral Thesis



Victoria University of Wellington School

School of Chemical and Physical Sciences


Robinson, W H; Smedley, S I